1,2,2,2-Tetrachlorethyl acrylate and methacrylate polymers and copolymers

ABSTRACT

A compound having the formula ##EQU1## wherein X is hydrogen, chlorine or a methyl group; homo and copolymers thereof and flame resistant articles made from such polymers.

This is a division application of Ser. No. 301,275 filed Oct. 27, 1972U.S. Pat. No. 3,882,169.

This invention relates to a new group of tetrahalo substituted alkylesters of α,β-monoethylenically unsaturated carboxylic acids, methods ofmaking the same homo- and copolymers thereof and articles made from thepolymers.

More particularly, the invention relates to tetrachloroalkyl acrylatesand methacrylates, especially 1,2,2,2-tetrachloroethyl acrylates andmethacrylates.

The 1,2,2,2-tetrachloroethyl acrylates and methacrylates have thefollowing formula: ##EQU2## wherein X may be hydrogen, chlorine or loweralkyl and preferably X is hydrogen, chlorine or methyl.

Heretofore compounds as above described have not been known, nor haveany methods of producing the same or of the homo- or copolymers thereof.

The compounds of the above formula (I) and especially the homo- andcopolymers of 1,2,2,2-tetrachloroethyl acrylate and methacrylate may beemployed as non-combustible organic glass, non-combustible foamedinsulating materials, components of hardenable adhesives, puttiesanalogous to "Dentakryl", noncombustible paints in the form ofsolutions, aqueous emulsions or suspensions. Non-combustible polymers,prepared according to this invention may be substituted for otherplastics in most instances where non-combustibility is required.

It is an object of the present invention to provide a novel group ofcompounds designated as tetrahalo substituted lower alkyl esters of α,β-monoethylenically unsaturated carboxylic acids.

It is another object of the invention to provide a novel group ofcompounds designated tetrachloroethyl acrylates and methacrylates.

It is still another object of this invention to provide a method ofmaking such compounds and also the homo- and copolymers thereof.

It is a further object of this invention to provide noncombustiblearticles prepared on the basis of such homo- and copolymers.

Further objects and advantages will become more apparent as thedescription of the invention proceeds.

Broadly speaking the instant invention includes the provision of a novelclass of compounds designated as tetrachloroethyl acrylates andmethacrylates, wherein the acrylate or methacrylate moiety thereof maycontain an additional chlorine substituent.

The above described acrylate and methacrylate esters may be prepared bytreatment of chloral with an acyl chloride of the formula ##EQU3##wherein x is as above described. Either the pure components or solutionsthereof may be employed in the reaction. The reaction may be acceleratedby the addition of small amounts of mineral acids, for example,concentrated sulfuric acid, hydrochloric acid and by the use of certainsalts, for instance, ferric chloride. The reaction can also be carriedout in the presence of an organic or inorganic base such astriethylamine, sodium carbonate and the like. The amount of mineralacid, salt or base used is however, not critical but should be betweenzero and 5% based on the weight of both reactants, usually between 0.04and 0.5%.

When a buffer is used herein or in the polymerization step, this may forexample be sodium bicarbonate, sodium acetate, or sodium dihydrogenphosphate in an amount of between 0.05% to about 1.0% based on theweight of the total reactants. Chain transfer agents which may be used,usually in an amount of between about 0.1% and about 2.0% based on thetotal monomer, include carbon tetrachloride, trichloroethylene,mercaptans, diisopropylxanthogen disulphide toluene and the like.

Where the synthesis is carried out in solution, those solvents which arenon-reactive with the reactants should be employed. The solvent shouldpreferably be anhydrous. Suitable solvents include benzene,diethylether, tetrachloromethane and the like. The solvent, when one isemployed, is used in an amount sufficient to form a workable reactionmedium, preferably in amounts between 50% and 100% based on the volumeof both reactants.

The compounds of the invention are preferably prepared by adding thereactants to a sufficient volume of reaction medium which can include asuitable liquid solvent, accelator, base, buffer etc. The reactants maybe brought into solution form by addition of the solvent, or they may bereacted by the addition thereto of a suitable liquid accelerator. Wherethe accelerator selected for use is a mineral salt, it is preferablethat the reactants be present in the form of their solution. Thereactants and accelerators may be used in anhydrous form and admixedwith a suitable stabilizer, such as hydroquinone. The order of additionof the reactants is not critical, although it is preferred that theaccelerator, when one is employed, be added to the mixture of solutionof reactants. The addition then may be carried out in increments or thetotal amount of accelerator may be added at once. The reaction isgenerally exothermic and is advantageously carried out in an ice bath.It may however, also be carried out at reflux temperatures. A preferredreaction temperature range is from 20° to 60°C. The time of reactionwill, in part, be determined by the temperature employed, the reactantsinvolved and whether or not an accelerator is used. The ratio of thereactants may be varied over a wide range, although ordinarily thereactants will be employed in about stoichiometric quantities,preferably amounting to 1:1 molar.

The homo- and copolymers of the novel compounds of the invention may beprepared by free radical polymerization in either bulk, suspension,solution of emulsion systems utilizing therefor procedures known to theart. Suitable free radical initiators for the homo- or copolymerizationinclude the free radicalsupplying polymerization catalysts yieldingoxygen under the conditions of polymerization, as represented by theinorganic and organic peroxygen or peroxide compounds. As examples ofsuch compounds, there may be mentioned hydrogen peroxide, metal andalkali metal peroxides such as sodium, potassium, barium and zincperoxide, diacyl peroxides such as diacetyl, dibenzoyl and dilauroylperoxide, dialkyl peroxides such as di-(tertiarybutyl) peroxide anddi-(tertiary-butyl) hydroperoxide, cyclohexene peroxide, inorganicperoxygen acids such as perboric, persulfuric and peracetic acid andtheir ammonium, sodium and potassium salts, in addition to redox systemssuch as potassium or ammonium persulfate-sodium bisulfite. Otheroxygen-yielding compounds or sources include atmospheric oxygen, ozoneand the like.

Azo type catalysts, i.e., compounds containing the azo linkage, may alsobe employed. As example of such catalysts there may be mentionedα,α'-azobis-(α,γ-dimethylvaleronitrile), α,α'-azobis-(α-methylbutyronitrile), α,α'-azobis(α-ethyl butyronitrile),α,α'-azo-diisobutyramide, dimethyl and diethyl, α,α'-azodiisobutyrate,and the like.

The preferred catalysts effective for the production of optimum resultsare the azo type, which may be employed along with an activator. Sometypical activators are amines, metabisulfites, ascorbic acid, Fe saltsand many other activators which are well known to those skilled in theart.

The polymerization will generally be carried out at a temperatureeffective to cause the initiator or catalyst to form free radicals andthus to propagate and maintain the reaction and preferably between 20°and 80°C. The catalyst may be employed in amounts ranging from 0.005 to5.0% by weight based on the weight of the monomers, at a temperature ofabout 20° to 100° C and preferably 45° to 80° C.

The reaction is preferably carried out in an inert atmosphere,conveniently under a blanket of nitrogen, argon or the like, and atatmospheric pressure. Also anhydrous conditions should be used.

After the polymerization is effected upon completion of the solution andthe heating period, the polymer may be observed to precipitate and maybe recovered by filtration or evaporation of the solvent. The foregoingis applicable when emulsion, suspension or solution polymerization iscarried out.

It will be understood that in carrying out the process of thisinvention, the known surface active agents, protective colloids,plasticizers, thickeners, and other additives may be added prior to,during or after the polymerization reaction is completed. Anionic,nonionic or cationic emulsifying agents may be employed. As examples ofnonionic agents which may be employed, there may be mentioned thecondensation products of a plurality of moles of ethylene oxide withorganic compounds containing at least 8 carbon atoms and a reactivehydrogen atom such as the water insoluble carboxylic and sulfonic acids,alcohols, thiols, phenols, hydroxy carboxylic acids, carboxy andsulfonic acid amides, primary and secondary amines andhydroxyalkylamines. As specific examples of such nonionic agents theremay be mentioned the reaction products of 1 mole of nonylphenol with 9to 100 E.O. (moles ethylene oxide), 1 mole of castor oil with 20 E.O., 1mole tall oil with 18 E.O., 1 mole of oleyl alcohol with 20 E.O., 1 moleof dodecyl mercaptan with 9 E.O., 1 mole of soybean oil amine with 10E.O., 1 mole of rosin amine with 32 E.O., 1 mole of cocoanut fatty acidamine with 7 E.O., 1 mole of dinonyl phenol with 15 E.O., 1 mole of oxotridecyl alcohol with 12 E.O., Pluronic L62 and the like.

Suitable anionic surface active agents include the sulfonic acids,sulfate esters, and phosphate esters (particularly the primary andsecondary phosphate esters and mixtures thereof) of the above mentionednonionic surface active agents as disclosed, for example, in U.S. Pat.Nos. 3,004,056 and 3,004,057. Other such anionic surface active agentsinclude alkylaryl sulfonic acids such as dodecylbenzene sulfonic acid,alkyl sulfates such as sodium M-methyltaurides of higher (C₁₀ to C₂₀)fatty acids, and isothionates such as sodium N-methylisothionate estersof higher (C₁₀ to C₂₀), fatty acids.

Protective colloids and/or thickening agents may also be employed ifdesired such as polyvinyl alcohol, copolymers such as the copolymer ofvinyl methyl ether and maleic anhydride, hydroxyethyl cellulose,carboxymethyl cellulose, natural gums and colloidal materials and thelike. Viscosities of up to 80,000 cps. or more may thereby be obtainedwhen required.

The order of addition of the monomers catalyst, emulsifier whereemployed, activator etc., is not critical. The monomers and catalyst,etc., may be added in increments or otherwise. It is preferred that aliquid medium be prepared from all of the monomers, catalyst andadditional agents and that thereafter polymerization be initiated.Polymerization is effected through the ethylenically unsaturated linkagein the monomers, i.e., vinyl polymerization.

When the tetrachloroethyl acrylate or methacrylate is copolymerized withanother monomer, said other monomer may be selected from among thosevinyl, diene and conjugated diene monomers which are operative tocopolymerize by the free radical mechanism. The vinyl monomer can be analkenyl or mono alkenyl aromatic monomer i.e., diolefin, conjugateddiolefin, vinyl aromatic or mono-ethylenically unsaturated monomer. Theratio of the monomers in the case of copolymerization may vary from 1:99to 99:1 and preferably from 1:50 to 50:1.

By the term "conjugated diene" it is meant to include typically,butadiene-1,3; 2-methyl-butadiene-1,3; 2,3-dimethyl butadiene-1,3;piperylene; 2-neopentylbutadiene-1,3; and other homologs ofbutadiene-1,3 and in addition, the substituted dienes, such as2-chlorobutadiene-1,3; 2-cyano-butadiene-1,3; the substituted straightchain conjugated pentadienes, the straight-and-branch-chain hexadienes,and others. The butadiene-1,3 hydrocarbons because of their ability toproduce particularly desirable polymeric materials, are preferredcomonomers.

As to the mono olefin any normal alpha olefin having at least 4 carbonatoms and no more than 22 carbon atoms, may be used, the C₄ -C₁₀ olefinsbeing preferred. Branched olefins such as 3 methyl butene-1, 3-methylhexene-1, 2-methyl butene-1,2,4,4-trimethyl pentene-1, 2-methylpentene-1 and 2,4,4-trimethyl pentene-2 are operative. Among other alphaolefins which are applicable are octene-1, hexene-1, decene-1,octadecene-1, hexadecene-1, dodecene-1,tetradecene-1, cicosene-1, andthe like.

By the term "monoalkenyl aromatic monomer" it is intended to includethose monomers wherein an alkenyl group is attached directly to anaromatic nucleus containing about 6 to about 10 carbon atoms. Thesemonomers may include alkyl, alkoxy and/or halo substituted compounds.Typical of these monomers are styrene, p-methylstyrene, α-methylstyrene,α-p-dimethyl styrene, α and β-bromovinyl benzene, α and β-chlorovinylbenzene, α,m-, or p-methoxy-vinyl benzene, o-p-diethyl styrene,p-chlorostyrene, isopropyl styrene, tert-butyl styrene,α-methyl-p-isopropyl styrene, α-chloro-p-methylstyrene, andα-p-dichlorostyrene and the like, and any mixtures thereof. Vinylnaphthalenes may also be used either alone, mixtures thereof or incombination with the styrene monomers. Because of its availability andability to produce desirable polymers and for other reasons, it ispreferred to use styrene as the monoalkenyl aromatic monomer. Thesechlorine-containing polymers can be used to impart flame retardancy tosynthetic resins and foams alike.

The alpha,beta-olefinically unsaturated nitriles or primary amides arepreferably the monoolefinically unsaturated nitriles having from 3 to 10carbon atoms such as acrylonitrile methacrylonitrile, ethacrylonitrileand the like. Most preferred are acrylonitrile and methacrylonitrile.

In the following examples and in the appended claims, all parts andproportions are by weight unless otherwise noted.

The following examples are illustrative and are not to be considered aslimiting.

Preparation of 1,2,2,2-tetrachloroethyl acrylate: EXAMPLE 1

In a reactor vessel 0.5 grams of concentrated sulfuric acid was added toa mixture of 102 grams of anhydrous chloral and 62.6 grams of acryloylchloride stabilized with hydroquinone. During the addition of themixture to the reactor, it was stirred and cooled with ice water. Areaction immediately takes place. After it had ceased the resulting darkproduct was fractionated under reduced pressure or partial vacuum. Themain fraction was collected in the amount of 107 grams at 63°C/0.5 Torrand then distilled five times through a descending condenser up tochromatographic purity. Distillation through an effective column isavoided because of the large loss due to polymerization. Refractiveindex and density of the fraction were as follows: n_(D) ²⁰ 1.4862; d₄²⁰ 1.4633; d₄ ⁵⁰ 1.4247. The composition determined by the elementalanalysis: C 25.95%, H 1.99% and Cl 58.53%. A standard calculated for1,2,2,2-tetrachloroethyl acrylate: C 25.24%, H 1.69% and Cl 59.62%

EXAMPLE 2

Into a vessel a solution consisting of 14.7 grams of chloral and 10.4grams of acryloyl chloride in 25 ml of benzene, 0.25 grams of anhydrousFeCl₃ was added. The reaction starts immediately and continues in therefluxing benzene. After the reaction was completed, the mixture wassteam-distilled and the lower layer of the condensate was separated,dried and fractionated under reduced pressure. Chromatographically pure1,2,2,2-tetrachloroethyl acrylate was obtained in the amount of 14.5grams.

Preparation of 1,2,2,2-tetrachloroethyl methacrylate: EXAMPLE 3

In a reactor vessel anhydrous FeCl₃ (0.25 grams) was added to a mixtureconsisting of 134 grams of anhydrous chloral and 95 grams ofmethacryloyl chloride, stabilized by hydroquinone. The mixture wasstirred and cooled in the reactor in ice water. The reaction occursquickly and after it had ceased, the resulting dark mixture wasfractionated under reduced pressure. The main fraction was distilled at70°C/0.4 Torr in the amount of 202 grams. It was refined by a threefolddistillation through a descending condenser to chromatographic purity.Refractive index and density of the fraction was as follows: n_(D) ²⁰1.4856, d₄ ²⁰ 1.4187, d₄ ⁵⁰ 1.3812. By the elemental analysis it wasdetermined: C 28.98%, H 2.48% and Cl 55.08%; calculated for1,2,2,2-tetrachloroethyl methacrylate: C 28.60%, H 2.40% and Cl 56.30%.

Preparation of the homo- and copolymers of the products of Examples 1 -3 EXAMPLE 4

A solution of 0.0065 grams of 2,2'-azobisisobutyronitrile in 5 grams of1,2,2,2-tetrachloroethyl acrylate (the product of Examples 1-2) wascharged into a glass ampoule, and cooled to -78°C. The ampoule wasflushed with nitrogen, sealed and placed into a temperature controlledbath heated to 60°C. A colorless, clear and elastic plug of the homopolymer thereof was formed after 20 hours. The plug burns in the flameof a gas burner, however, when removed from the flame, burning of themolten mass did not continue. The polymer did not dissolve in aromatichydrocarbons, chlorinated hydrocarbons, alcohols or ketones, and itsdensity, determined pycnometrically, was d₄ ²⁰ 1.7029.

EXAMPLE 5

A mixture of 2 grams of 1,2,2,2-tetrachloroethyl acrylate, 2 grams ofstyrene and 0.01 grams of benzoyl peroxide was prepared forpolymerization as in Example 4. The contents of the ampoule arepolymerized at 60°C for 20 hours to a colorless, slightly opalescent,elastic plug. The polymer dissolved neither in aromatic nor inchlorinated hydrocarbons and its inflammability was lower than that ofpure polystyrene.

EXAMPLE 6

A solution of 3 grams of 1,2,2,2-tetrachloroethyl acrylate and 0.013grams of 2,2'-azobisisobutyronitrile in 7 ml of benzene was homopolymerized in a glass dilatometer at a temperature 50°C to about 10percent conversion of the monomer. After the calculated volume had beenachieved, the content of the dilatometer was poured into a flaskcontaining 80 ml of ethanol. The colorless polymer precipitated (0.35grams), and dissolved in benzene as well as in tetrachloromethane.

EXAMPLE 7

A solution of 0.0065 grams of 2,2'-azobisisobutyrinitrile in 5 grams of1,2,2,2-tetrachloroethyl methacrylate (the product of Example 3) wasprepared for polymerization in the same way as described in Example 4.After 20 hours of heating at 60°C, a hard plug was formed. The densityof the polymer was d₄ ²⁰ 1.6014. The polymer dissolved in aromatic andchlorinated hydrocarbons and ketones but did not dissolve in aliphatichydrocarbons, alcohols or in water. It burns in the flame of a gasburner, but when removed from the flame, the molten mass extinguishes.

EXAMPLE 8

A glass ampoule was charged with 7 grams of isoprene, 2 grams of1,2,2,2-tetrachloroethyl methacrylate, 0.05 grams of dodecylmercaptan,0.04 grams of potassium persulfate, 0.5 grams of "Mersolate" (weight ofa dry substance), and 18 grams of distilled water. The ampoule wascooled to -78°C, evacuated, sealed under vacuum and then placed into acontainer rotating in a water bath at a temperature 50°C. After 6 hoursa latex forms and was poured into 200 ml of ethanol, which had beenpreviously acidified with 0.5 ml of concentrated hydrochloric acid. Thewhite polymer precipitated (2.7 grams), was rubberlike and soluble inbenzene.

What is claimed:
 1. A polymeric composition comprising approximately byweight (a) 100 to 1% of a monomer derived from the1,2,2,2,-Tetrachloroethyl ester of the formula ##EQU4## wherein X isselected from the group consisting of hydrogen, chlorine and methyl,said monomer (a) being copolymerized with (b) 0 to 99% of a monomerselected from the group consisting of olefins, diolefins, conjugateddiolefins, a monoalkenyl aromatic moiety and a nitrogenous moiety.
 2. Apolymeric composition according to claim 1 containing 100% of component(a).
 3. A polymeric composition according to claim 1 wherein component(b) is included in amounts of about 1 to 50% by weight.
 4. A polymericcomposition according to claim 1 wherein component (b) is selected fromthe group consisting of a 1,4 conjugated C₄₋₉ diene, a vinyl arylalkenylmonomer, an ester of a α,β-monoethylenically unsaturated carboxylic acidand a primary amide of an B-monoethylenically unsaturated carboxylicacid.
 5. A polymeric composition according to claim 4 wherein said dieneis an isoprene or butadiene, said vinyl aryl alkenyl monomer is a vinyltoluene, said carboxylic acid ester is a lower alkyl acrylate ormethacrylate and said primary amide is acrylamide.
 6. A method forpreparing the composition according to claim 1 comprising polymerizingcomponents a) and b) in the presence of a free radical catalyst at atemperature of about 30° to about 100°C.
 7. A method according to claim6 which comprises carrying out said polymerization in a liquid medium.8. A flame retardant material containing as an essential ingredient apolymer defined in claim 1 in an amount sufficient to preventflammability.
 9. A flame retardant synthetic resin carrier containing anamount of the polymer as defined in claim 1 effective to preventflammability.
 10. A flame retardant synthetic foamed resinous materialcontaining an amount of the polymer according to claim 1 effective toprevent flammability.